Ce(III)/Ce(IV) in methanesulfonic acid as the positive half cell of a redox flow battery

The characteristics of the Ce(III)/Ce(IV) redox couple in methanesulfonic acid were studied at a platinum disk electrode (0.125 cm²) over a wide range of electrolyte compositions and temperatures: cerium (III) methanesulfonate (0.1–1.2 mol dm⁻³), methanesulfonic acid (0.1–5.0 mol dm⁻³) and electrolyte temperatures (295–333 K). The cyclic voltammetry experiments indicated that the diffusion coefficient of Ce(III) ions was 0.5 × 10⁻⁶ cm² s⁻¹ and that the electrochemical kinetics for the oxidation of Ce(III) and the reduction of Ce(IV) was slow. The reversibility of the redox reaction depended on the electrolyte composition and improved at higher electrolyte temperatures. At higher methanesulfonic acid concentrations, the degree of oxygen evolution decreased by up to 50% when the acid concentration increased from 2 to 5 mol dm⁻³. The oxidation of Ce(III) and reduction of Ce(IV) were also investigated during a constant current batch electrolysis in a parallel plate zinc–cerium flow cell with a 3-dimensional platinised titanium mesh electrode. The current efficiencies over 4.5 h of the process Ce(III) to Ce(IV) and 3.3 h electrolysis of the reverse reaction Ce(IV) to Ce(III) were 94.0 and 97.6%, respectively. With a 2-dimensional, planar platinised titanium electrode (9 cm² area), the redox reaction of the Ce(III)/Ce(IV) system was under mass-transport control, while the reaction on the 3-dimensional mesh electrode was initially under charge-transfer control but became mass-transport controlled after 2.5–3 h of electrolysis. The effect of the side reactions (hydrogen and oxygen evolution) on the current efficiencies and the conversion of Ce(III) and Ce(IV) are discussed.     

Adsorptive removal of hexavalent chromium using sawdust: Enhancement of biosorption and bioreduction

Simultaneous biosorption and bioreduction experienced by Cr(VI) species were initially validated by mixing 500 µM of Cr(VI) with 0.20 g of sawdust biosorbent. Accordingly, a complete disappearance of Cr(VI) species with emergence of 25% of Cr(III) ions was recorded; evidencing that both processes transpired simultaneously. An increase in the initial Cr(VI) concentration to 1500 µM could further induce more reduced Cr(VI) concentration. The enhancement of Cr(VI) biosorption and bioreduction was found to occur upon increasing the sawdust dosage to 4 g L^?1 and decreasing the solution pH to 2. However, the presence of a Zn(II) co-pollutant at 2500 µM had deteriorated the removal of Cr(VI) species.     

Electrolytic oxidation of Ce(III) in nitric acid and sulfuric acid media using a flow type cell

The electrochemical oxidation behavior of Ce(III) in nitric acid and sulfuric acid media with various concentrations and compositions were investigated by cyclic voltammetry (CV) and potentiostatic electrolysis. In nitric acid media, the peak potential separation for the redox reactions of the Ce(III)/Ce(IV) couple shifted to base side with the increasing concentration of nitric acid from 1 to 6 M. The kinetics of the Ce(III)/Ce(IV) couple is rapid in high concentration nitric acid. The formal potential is independent of both proton and nitrate concentrations while the standard rate constant increases with added protons but is independent of nitrate concentration. Constant-potential electrolysis also shows that a high proton concentration is electrochemically favorable for the electron transfer of the Ce(III)/Ce(IV) couple and for a high Ce(IV) yield in nitric acid media. The current efficiency was ca. 75% for the oxidation process of Ce(III) at 298 K. A Ce(IV) yield of ca. 80% was achieved for the electrolysis of 100 mM Ce(III) in 6 M HNO₃ solution. In sulfuric acid media, the peak potential separation for the redox reactions of the Ce(III)/Ce(IV) couple shifted to noble side with rising concentration of sulfuric acid from 0.1 to 2 M and then shifted to base side with further increase in the concentration. A Ce(IV) yield of ca. 95% was achieved for the potentiostatic electrolysis of 100 mM Ce(III) in 3 M H₂SO₄ solution.     

Sorption equilibrium of Cr(VI) ions on oak wood charcoal (Carbo Ligni) and charcoal ash as low-cost adsorbents

The aim of this study is to demonstrate the potential of oak wood charcoal (WC) and oak wood charcoal ash (WCA) as a low-cost adsorbent for environmental protection applications of Cr(VI) ion. The influence of contact time, solution pH, initial metal concentration, amount of adsorbent and ionic strength on the removal of Cr(VI) ion was studied. The adsorption of Cr(VI) with (WC) and (WCA) was investigated in a batch arrangement. The Cr(VI) ions sorbed onto the adsorbents were determined by a UV-Visible Spectrophotometer. The sorption of Cr(VI) on the adsorbent surface depends strongly on the pH and Cr(VI) ion-sorption increased with a decreasing pH until pH 2 and increase in the concentration of this metal in solution phase. The adsorption of Cr(VI) was higher between pH 2.0 and 2.5 for both adsorbents. The Freundlich adsorption isotherm was used to describe observed sorption phenomena. The maximum adsorption capacity of 30.10 mg of Cr(VI)/g for (WC) and 46.17 mg of Cr(VI)/g for (WCA) was obtained at pH of 2 and 2.5 respectively.     

Electrochemical sensor-based gold nanoparticle/poly(aniline-co-o-toluidine)/graphene oxide nanocomposite modified electrode for hexavalent chromium detection: a real test sample

This paper presents the fabrication of poly(aniline-co-o-toluidine)/graphene oxide nanocomposite with a general abbreviation [PANI-co-PoT/GO_a–e] by well-known in-situ oxidative polymerization method with ultrasonic assistance. These materials were based on variable loading of GO when prepared. The chemical structures of the composite materials were confirmed by characterization technique. The FE-SEM and TEM micrographs were used to investigate the morphological features. Furthermore, FT-IR, XRD, TGA, and electrical conductivity measurements were utilized to estimate its complete performance. All nanocomposites showed CDT_max values in the range of 287.25–463.51 ºC which is significantly higher than that observed for pure copolymer (204.79 ºC). The main focus of this paper is to study the electroselective application using gold nanoparticle as a coating. A steady electroactive modified electrode [AuNPs/PANI-co-PoT/GO] was effectively prepared on a gold electrode (Au) surface using an electroadsorption process for the determination of Cr(VI). The electrochemical attitude of the modified sensor toward the reduction of Cr(VI) was studied by a square wave voltammetry (SWV) and a cyclic voltammetry (CV) technique. The AuNPs/PANI-co-PoT/GO modified electrode displayed a perfect electrochemical activity toward the reduction of Cr(VI). Using an SWV method, the modified electrode gave a linear response to Cr(VI) through the concentration range 5–500 µM with a limit of detection 0.0215 µM. The suggested sensor displayed good stability, sensitivity and selectivity and has exhibited potential for the detection of Cr(VI) in real samples.     

Reduction of Cr(VI) to Cr(III) and removal of total chromium from wastewater using scrap iron in the form of zerovalent iron(ZVI): Batch and column studies

This work experimentally investigates Cr(VI) reduction to Cr(III) using waste scrap iron in the form of zerovalent iron (ZVI) collected from the mechanical workshop of the Institute, both in batch and continuous operation. The reduction of Cr(VI) to Cr(III) was found to be complete (～100%) depending on the experimental conditions. Lower pH values favour Cr(VI) reduction. Two concurrent reactions take place, that is reduction of Cr(VI) by Fe⁰ (ZVI) and by Fe²⁺ generated due to H⁺ corrosion of iron. Maximum around 22%, 11% and 2% Cr(III) remained dissolved in solution while the experiments were carried out at initial pH of 2, 4.67 and 7. Higher ZVI loading increases Cr(VI) reduction rate, however, consumption of iron is noted to be higher. The results indicate that the bed is exhausted rapidly at higher pH, initial Cr(VI) concentration and flow rate. This is attributable to predominance passivation of ZVI surface forming Cr(III)–Fe(III)‐oxide layer. SEM analysis of ZVI before and after the experiments confirms formation of passive oxide on iron surface is responsible for deterioration of Cr(VI) reduction efficiency due to its blanketing effect.     

Composition and behaviour of cerium films on galvanised steel

The composition and corrosion performance of galvanised steel treated by immersion in cerium nitrate solution was investigated by electrochemical techniques and surface analysis. The surface film consists of a mixture of Ce(III) and Ce(IV) compounds, being very rich in Ce(III) in the first instants of the deposition process and becoming gradually enriched in the more oxidised form, Ce(IV). The presence of this film on the surface hinders the corrosion reaction by reducing the rate of both the cathodic and the anodic reactions. The film becomes thicker but more uneven when the time of film growth increases, with the development of defects in the film, which in contact with electrolyte behaves anodic with respect to the covered areas of the surface. These thicker films have revealed lower resistance to corrosion initiation.     

Capacity of Cr(VI) reduction in an aqueous solution using different sources of zerovalent irons

Zerovalent iron (ZVI) has drawn intense interest as an effective and inexpensive tool to enhance degradation of various environmental contaminants. Reduction of Cr(VI) to Cr(III) by ZVI merits environmental concern as a hazardous species is transformed into a non-hazardous one. Objectives of this research were to assess kinetics and capacity of Cr(VI) reduction by different sources of ZVIs, of which chemical parameters can base in situ application of ZVI to treat Cr(VI) contaminated water. Reduction kinetics were first-order and rapid showing that 50% of the initial Cr(VI) was reduced within 7.0 to 347 min depending on Cr(VI) concentration, temperature and ZVI source. The reduction rates were increased with decreasing the initial Cr(VI) concentrations and increasing the reaction temperatures. The J ZVI (Shinyo Pure Chemical Co., Japan) was more effective in Cr(VI) reduction than PU (Peerless Metal Powders, USA). The maximum reduction capacities of J and PU ZVIs at 25°C were 0.045 and 0.042 mmol g⁻¹ Fe⁰, respectively. A relatively higher value of the net reaction energy (E _a ) indicated that Cr(VI) reduction by ZVI was temperature dependent and controlled by surface properties of ZVI. Chemical parameters involved in the Cr(VI) reduction by ZVI such as temperature quotient, kinetic rates, and stoichiometry indicated that the ZVI might be effective for in situ treatment of the Cr(VI) containing wastewater.     

Modulated Cr(III) oxidation in KOH solutions at a gold electrode: Competition between disproportionation and stepwise electron transfer

The electrochemical oxidation of aqueous Cr(III) was examined using cyclic voltammetry with a polycrystalline Au electrode in KOH solutions of varying pH and Cr(III) concentration. The mechanism and kinetics for the oxidation of Cr(III) is a quasi-reversible diffusion-controlled reaction and is largely dependent on the solution pH. The reaction mechanism is initiated by an irreversible electrochemical electron transfer to form Cr(IV) which is the rate-determining step (RDS). Following the RDS, subsequent oxidation of Cr to its hexavalent state occurs by the disproportionation of Cr(IV) at low KOH concentrations and electron transfer at high KOH concentrations due to the involvement of OH⁻ in the disproportionation reaction. As the solution pH increases, the Cr(III) oxidation peak potential shifts negatively owing to the involvement of OH⁻ in the RDS. The competitive adsorption of OH⁻ and CrO₂⁻ on the electrode surface also plays an important role in the oxidation behavior.     

Reduction of hexavalent chromium by copper

The galvanic reaction of metallic copper in Cr(VI)-laden aqueous solutions of varying pH was examined by in situ u.v.–visible spectrophotometry, rotating disc electrode chronopotentiometry and cyclic voltammetry. The galvanic reaction in 0.2 M H₂SO₄ solutions was pseudo first order in Cr(VI) concentration. Experiments with both magnetically stirred solutions and a copper mesh or a copper film in a rotating disc electrode configuration revealed the reaction to be diffusion-controlled with respect to Cr(VI) transport to the copper surface. Finally, cyclic voltammetry data in Cr(VI)-laden media of varying pH underline the important role of protons in the galvanic reaction.     

The influence of platinum (phase) oxide on the electrode kinetics of the manganese(III)/manganese(II) and cerium(IV)/cerium(III) redox couples in sulphuric acid

The kinetics of the Ce(III)/Ce(IV) and Mn(II)/Mn(III) redox reactions (both oxidation and reduction) were followed at a rotating Pt disc electrode, on which known amounts of platinum oxide (type II) had been formed. Oxide film inhibits both anodic and cathodic reactions, but to different extents. There is no systematic decrease in i₀ with increase in film thickness suggesting that electron tunnelling is unimportant under these conditions but that electron exchange takes place with the oxide itself. The inhibiting effect of type II oxide is seen even when it is present in sub-monolayer amounts, and this and other effects suggest that the overall behaviour of the system cannot be simply represented, for example in terms of a semi-conducting oxide.     

Simultaneous degradation of RhB and reduction of Cr(VI) by MIL-53(Fe)/Polyaniline (PANI) with the mediation of organic acid

MIL-53(Fe)/polyaniline (PANI) composite was prepared by in situ depositing PANI on the surface of MIL-53(Fe) and their catalytic performances on the simultaneous removal of RhB and Cr(VI) were investigated. The elimination efficiency of both RhB and Cr(VI) reached more than 98% under pH=2 where hydrochloric acid and citric acid were used to adjust the pH. The results indicated that MIL-53(Fe)/PANI revealed an obvious pH response to the degradation of RhB, while citric acid promoted the Cr(VI) photoreduction. UV-Vis spectra, EIS, and photocurrent response experiments showed that MIL-53(Fe)/PANI had a better light response and carrier migration ability than MIL-53(Fe). The transient absorption spectra also exhibited that the lifetimes of photo-generated carriers were prolonged after the conductive polymer deposition on the MIL-53(Fe) surface. Scavenger experiments demonstrated that the main active species were ·O₂^- and OH. Combined with activity evaluation results, and the possible photocatalytic mechanism of MIL-53(Fe)/PANI on RhB oxidation and Cr(VI) reduction was proposed. The addition of conductive polymer can effectively improve the light response of the catalyst under acidic conditions, and meanwhile citric acid also provided a new mediation for the synergistic degradation of multiple pollutants. Good activity and stability of the catalysts made the scale-up purification of acid water feasible under UV-Vis light.     

Electrochemical comparison of IrO2 prepared by anodic oxidation of pure iridium and IrO2 prepared by thermal decomposition of H2IrCl6 precursor solution

Surface redox activities, oxygen evolution reaction (OER), oxidation of formic acid (FA), and anodic stability were investigated and compared for IrO₂ electrodes prepared by two techniques: the thermal decomposition of H₂IrCl₆ precursor (TDIROF) and the anodic oxidation of metallic iridium (AIROF). Surface redox activities involved on the AIROF were found to be much faster than those involved on the TDIROF. Concerning the oxygen evolution reaction, both films show a similar mechanism and specific electrocatalytic activities. The situation seems to be different for FA oxidation. In fact, on TDIROF, the oxidation of FA and the OER compete involving the same surface redox couple Ir(VI)/Ir(IV) contrary to FA oxidation on AIROF, where the Ir(V)/Ir(IV) surface redox couple is involved. Finally, electrode stability measurements have shown that contrary to TDIROF, which are very stable under anodic polarization, the AIROF are rapidly corroded under anodic treatment. This corrosion is enhanced even further in the presence of formic acid.     

A study of the Ce(III)/Ce(IV) redox couple for redox flow battery application

In this study, the electrochemical behavior of the Ce(III)/Ce(IV) redox couple in sulfuric acid medium with various concentrations and the influence of the operating temperature were investigated. A change of the concentration of sulfuric acid mainly produced the following two results. (1) With an increase of the concentration of sulfuric acid the redox peak currents decreased. (2) The peak potential separation for the redox reactions increased with rising concentration of sulfuric acid from 0.1 to 2 M and then decreased with further increase of the concentration. Elevated temperature was electrochemically favorable for Ce(III)/Ce(IV) couple, which caused an increase of the peak currents for the redox reactions and a decrease of the peak potentials separation. Constant-current electrolysis shows that the current efficiency was 73% for the oxidation process of Ce(III) and 78% for the reduction process at 298 K, and could be improved by elevating the temperature. The open-circuit voltage of the Ce-V cell, after full charging, remained constant at 1.870±0.005 V for more than 48 h, and is about 29% higher than that of the all-vanadium batteries. The coulombic efficiency was approximately 87%, showing that self-discharge of the Ce-V battery was small. The preliminary exploration shows that the Ce(III)/Ce(IV) couple is electrochemically promising for redox flow battery (RFB) application.     

改性镍铁渣吸附剂对Cr(VI)吸附性能的影响及机理分析

以镍铁渣为原料,加入硝酸和表面活性剂对其矿物相改性,制备改性镍铁渣吸附剂,考察表面活性剂种类、十六烷基三甲基溴化铵(CTAB)掺量、吸附剂掺量、溶液初始pH值、Cr(VI)浓度对Cr(VI)吸附效果的影响。结果表明:镍铁渣经改性后可制得结构疏松、比表面积高达180.6 m²/g的无定形SiO₂;改性镍铁渣对Cr(VI)的吸附率在10 min内可达到90%,吸附等温线符合Langmuir模型,最大理论吸附容量为42.55 mg/g,吸附动力学符合拟二级动力学模型。改性镍铁渣吸附剂对Cr(VI)的吸附机理主要是物理吸附和氧化还原,即吸附剂表面范德华力将HCrO ^-₄吸附至吸附剂表面,CTAB提供的电子对将Cr(VI)还原为Cr(III)。对镍铁渣改性获得的高比表面积无定形SiO₂不仅可以有效吸附净化Cr(VI),同时可以实现镍铁渣资源化利用,达到以废治污的目的,具有良好的环境效应和经济效益。     

Use of gaseous Cr species to diagnose surface and bulk process for O2 reduction in solid oxide fuel cells

Oxygen reduction reactions on Sr-doped LaMnO₃ (LSM), Sr-doped La(Co,Fe)O₃ (LSCF) and Pt electrodes have been investigated in the absence and presence of gaseous Cr species at 900 °C in air. Gaseous Cr species were introduced by using chromia-forming alloy interconnect in contact with the electrode. In the presence of gaseous Cr species, the electrode processes for the O₂ reduction on LSM and Pt electrode were significantly inhibited while on LSCF electrodes, the inhibiting effect was much smaller. It has been shown that gaseous Cr species primarily inhibited the electrode surface process of the O₂ reduction reaction and the inhibiting effect can be quantitatively related to the oxygen diffusion coefficient of the electrode material. The results demonstrated that gaseous Cr species can be used to distinguish between the surface and bulk process kinetics for the O₂ reduction reaction under solid oxide fuel cells operation conditions.     

Comparison of ethylene polymerization catalyzed over Cr(VI)/silica and Cr(II)/silica catalysts

Summary Ethylene polymerization and the morphology of produced high density polyethylene (HDPE) catalyzed over. Cr(VI)/silica and Cr(II)/silica were studied. Cr/silica catalyst with Cr loading of 1 wt % has been prepared by impregnating an aqueous solution of CrO₃ onto silica having specific surface area of 301 m²/g and pore volume of 1.64 ml/g. The rate profiles and the morphologies of polyethylene polymerized over Cr(VI) and Cr(II)/silica were different. The process of active site formation influences the rate profiles. The shape of polyethylene particles polymerized with Cr(II)/silica resembled the original shape of catalyst particles. However, Cr(VI)/silica catalyst particles were fractured inhomogeneously during the polymerization. The variation of molecular weight and molecular weight distribution at various polymerization times indicated that the formation of active sites of Cr(VI)/silica was accomplished gradually during polymerization.     

油水分层流条件下腐蚀动力学特性模拟

当石油输送管道内处于油水分层流条件时,管道底部与酸性水层接触极易造成内腐蚀,严重威胁管道安全,传统的静止和单相流条件的腐蚀预测方法已不能指导管道的安全运行,而多相流动、离子传质、化学反应及电极动力学等多种不同尺度的物理化学过程对多相流腐蚀预测提出了挑战。本文基于多相流动特性及电化学腐蚀特性的耦合机理提出了分层流条件下腐蚀动力学模型,首先建立油水三层流传质计算模型,进而基于溶液区域和产物膜内部的传质计算,依据阴阳极电化学反应电流密度与传质通量之间的平衡关系,形成多相流条件下腐蚀预测方法。探究了离子传质、电极反应以及产物膜动态生长的耦合过程对腐蚀行为的作用机理,揭示了CO₂分压、温度对腐蚀发展规律的影响机制。研究发现温度、CO₂分压的改变会导致平衡反应方向的移动,从而改变离子浓度;离子的扩散系数是决定传质系数变化的内在原因;腐蚀速率的变化规律由产物膜生长和电极反应两种因素共同决定：腐蚀产物膜的生长会阻碍反应离子的传质效应,从而抑制腐蚀;而离子浓度的升高或传质增强会加快电极反应,促进腐蚀。     

The oxidation of trivalent chromium at the reconstructed Au(100) electrode

The electro-oxidation of Cr(III) to Cr(VI) species at the reconstructed Au(100) electrode has been investigated in a highly alkaline solution. The subsequent comparison of the results obtained with those at Au(111) electrode points to the structural sensitivity of this oxidation process related to different adsorbability of OH⁻ anions on both electrodes. Finally, it was found that the addition of Cr(III) ions does not shift the reconstruction peak to less positive values of potential indicating that for Au(100) electrode the oxidation process under consideration has no impact on the lifting of the surface reconstruction.